EP1793798A1 - Photo-stable cosmetic or dermatological compositions - Google Patents
Photo-stable cosmetic or dermatological compositionsInfo
- Publication number
- EP1793798A1 EP1793798A1 EP05786945A EP05786945A EP1793798A1 EP 1793798 A1 EP1793798 A1 EP 1793798A1 EP 05786945 A EP05786945 A EP 05786945A EP 05786945 A EP05786945 A EP 05786945A EP 1793798 A1 EP1793798 A1 EP 1793798A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- derivative
- use according
- formula
- alkyl
- cosmetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000002537 cosmetic Substances 0.000 title claims abstract description 42
- -1 amino-substituted 2-hydroxybenzophenone Chemical class 0.000 claims abstract description 63
- 239000004904 UV filter Substances 0.000 claims abstract description 22
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 230000005855 radiation Effects 0.000 claims abstract description 12
- WMJBVALTYVXGHW-UHFFFAOYSA-N 3,3-diphenylprop-2-enoic acid Chemical compound C=1C=CC=CC=1C(=CC(=O)O)C1=CC=CC=C1 WMJBVALTYVXGHW-UHFFFAOYSA-N 0.000 claims abstract description 7
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical class C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 11
- XNEFYCZVKIDDMS-UHFFFAOYSA-N avobenzone Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(C(C)(C)C)C=C1 XNEFYCZVKIDDMS-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 5
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- HEOCBCNFKCOKBX-RELGSGGGSA-N (1s,2e,4r)-4,7,7-trimethyl-2-[(4-methylphenyl)methylidene]bicyclo[2.2.1]heptan-3-one Chemical compound C1=CC(C)=CC=C1\C=C/1C(=O)[C@]2(C)CC[C@H]\1C2(C)C HEOCBCNFKCOKBX-RELGSGGGSA-N 0.000 claims description 3
- OIQXFRANQVWXJF-QBFSEMIESA-N (2z)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical class CC1(C)C2CCC1(C)C(=O)\C2=C/C1=CC=CC=C1 OIQXFRANQVWXJF-QBFSEMIESA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 150000007942 carboxylates Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229960004697 enzacamene Drugs 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- GXENJADUDUQAJG-UHFFFAOYSA-N 2-cyano-2-fluoren-9-ylideneacetic acid Chemical class C1=CC=C2C(=C(C#N)C(=O)O)C3=CC=CC=C3C2=C1 GXENJADUDUQAJG-UHFFFAOYSA-N 0.000 claims description 2
- GLDPVJQEQVXIMR-UHFFFAOYSA-N 2-fluoren-9-ylidenepropanedioic acid Chemical compound C1=CC=C2C(=C(C(O)=O)C(=O)O)C3=CC=CC=C3C2=C1 GLDPVJQEQVXIMR-UHFFFAOYSA-N 0.000 claims description 2
- 244000269722 Thea sinensis Species 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- 229940087603 grape seed extract Drugs 0.000 claims description 2
- 235000002532 grape seed extract Nutrition 0.000 claims description 2
- 235000009569 green tea Nutrition 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 230000003381 solubilizing effect Effects 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 239000001717 vitis vinifera seed extract Substances 0.000 claims description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical class CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 65
- 239000006071 cream Substances 0.000 description 21
- 239000003921 oil Substances 0.000 description 18
- 239000006096 absorbing agent Substances 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- 239000006210 lotion Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 6
- 239000002304 perfume Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 5
- 235000013336 milk Nutrition 0.000 description 5
- 210000004080 milk Anatomy 0.000 description 5
- 239000002453 shampoo Substances 0.000 description 5
- 230000000475 sunscreen effect Effects 0.000 description 5
- 239000000516 sunscreening agent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002781 deodorant agent Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000825 pharmaceutical preparation Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 230000037072 sun protection Effects 0.000 description 4
- LALVCWMSKLEQMK-UHFFFAOYSA-N 1-phenyl-3-(4-propan-2-ylphenyl)propane-1,3-dione Chemical compound C1=CC(C(C)C)=CC=C1C(=O)CC(=O)C1=CC=CC=C1 LALVCWMSKLEQMK-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000001166 anti-perspirative effect Effects 0.000 description 3
- 239000003213 antiperspirant Substances 0.000 description 3
- 229960000601 octocrylene Drugs 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HIPQTCQUXOFTFI-UHFFFAOYSA-N 2-methoxy-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(OC)C(=O)C1=CC=CC=C1 HIPQTCQUXOFTFI-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003788 bath preparation Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- FDATWRLUYRHCJE-UHFFFAOYSA-N diethylamino hydroxybenzoyl hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1O FDATWRLUYRHCJE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000000278 gas antisolvent technique Methods 0.000 description 2
- 125000005908 glyceryl ester group Chemical group 0.000 description 2
- 239000008266 hair spray Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000077 insect repellent Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000008194 pharmaceutical composition Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001046 rapid expansion of supercritical solution Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002047 solid lipid nanoparticle Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 235000015961 tonic Nutrition 0.000 description 2
- 230000001256 tonic effect Effects 0.000 description 2
- 229960000716 tonics Drugs 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000008307 w/o/w-emulsion Substances 0.000 description 2
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006433 1-ethyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000006026 2-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- ZYASLTYCYTYKFC-UHFFFAOYSA-N 9-methylidenefluorene Chemical class C1=CC=C2C(=C)C3=CC=CC=C3C2=C1 ZYASLTYCYTYKFC-UHFFFAOYSA-N 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 108091005932 CCKBR Proteins 0.000 description 1
- 208000001840 Dandruff Diseases 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 244000018716 Impatiens biflora Species 0.000 description 1
- 244000208060 Lawsonia inermis Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical class C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229960005193 avobenzone Drugs 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003581 cosmetic carrier Substances 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004090 cyclononenyl group Chemical group C1(=CCCCCCCC1)* 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007854 depigmenting agent Substances 0.000 description 1
- 230000035617 depilation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229960001679 octinoxate Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001092 precipitation with compressed antisolvent Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002437 shaving preparation Substances 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940045990 sodium laureth-2 sulfate Drugs 0.000 description 1
- GUQPDKHHVFLXHS-UHFFFAOYSA-M sodium;2-(2-dodecoxyethoxy)ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOS([O-])(=O)=O GUQPDKHHVFLXHS-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/066—Multiple emulsions, e.g. water-in-oil-in-water
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/415—Aminophenols
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
- A61K8/9783—Angiosperms [Magnoliophyta]
- A61K8/9789—Magnoliopsida [dicotyledons]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/16—Emollients or protectives, e.g. against radiation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances
Definitions
- the present invention relates to the use of a specific stabilizing agent (a) for improving the stability with respect to UV radiation of a cosmetic or dermatological composition
- a specific stabilizing agent (a) for improving the stability with respect to UV radiation of a cosmetic or dermatological composition
- a UV filter combination of at least one dibenzoylmethane derivative (b) and of at least one specific amino-substituted 2-hydroxybenzophenone derivative (c).
- sunscreen formulations which include materials which are in ⁇ tended to counteract UV radiation, thereby inhibiting the said undesired effects on the skin.
- a particular advantageous family of UV-A screening agents is currently com ⁇ posed of dibenzoylmethane derivatives and in particular 4-tert-butyl-4'-methoxydibenzoyl- methane; this is because these derivatives exhibit a high intrinsic absorbance.
- Dibenzoyl- methane derivatives are well known per se as screening agents actives in the UV-A region, and are disclosed in particular in FR-A-2 326 405, FR-A-2 440 933 and EP-A-O 114 607.
- 4-tert-butyl-4'-methoxydibenzoylmethane is currently offered for sale under the trademark of "Parsol 1789" by DSM.
- dibenzoylmethane derivatives are relatively sensitive to UV radiation (in particular UV-A radiation), AND more specifically, that they have an unfortunate tendency to more or less rapid decomposition under the effect of the latter.
- UV radiation in particular UV-A radiation
- this substantial lack of photochemical stability of dibenzoylmethane derivatives with respect to UV radiation does not make it possible to guarantee constant protection during prolonged exposure to the sun, so that repeated sun screen applications at regular and frequent intervals have to be carried out by the user in order to obtain effective protection of the skin against UV radiation.
- the photostabilization of dibenzoylmethane derivatives with respect to UV radiation con ⁇ stitutes a problem, which has not yet been solved until now in a completely satisfactory manner.
- the present invention relates to the use of an effective photo-stabilizing amount of stabilizing agent (a) selected from a diphenylacrylate UV filter (ai), a benzyl idene camphor derivative (a 2 ), an organosiloxane comrising benzalemalonate groups (a 3 ), a fluoren derivative (a 4 ), a naphthalene dicarboxylic acid derivative (a 5 ) a natural occurring stabilizer (a 6 ); and a phenolic antioxidant (a 7 ); for improving the stability with respect to UV radiation of a cosmetic or dermatological com ⁇ position comprising a UV filter combination of at least one dibenzoylmethane derivative (b) and of at least one specific amino-substituted 2-hydroxybenzophenone derivative (c).
- a a diphenylacrylate UV filter
- a 2 a benzyl idene camphor derivative
- the diphenylacrylate UV filter (ai) which is used in the present invention for the stabilization of cosmetic or dermatological composition is preferably selected from 2-ethylhexyl 2- cyano,3,3-diphenylacrylate which corresponds to the
- Suitable benzylidene camphor derivatives (a 2 ) are disclosed in US-A-5,605,680.
- p-methylbenzylidene camphor is used in the present invention as component (a 2 ).
- the organosiloxane comprising benzalemalonate groups (a 3 ) preferably correspond to the formula
- R is CrCi O alkyl; phenyl; or 3,3,3-trifluoropropyl, at least 80% of the number of the R radicals being methyl radicals; r is an integer rom O to 200; s is an integer rom 0 to 50 u is an integer from 1 to 20; t is an integer from 0 to 20; wherein t + u is equal to or greater than 3; and.
- a and/or B is a benzalmalonate radical.
- A is preferably the radical of formula (2c) X .5 , wherein Ri and R 2 are each hydrogen; OH; trimethylsiloxy; CrC 6 alkyl; CrC 6 alkoxy; or a radical of the
- R 4 with the proviso that one of the radicals Ri and R 2 is the bivalent radical of formula (2d);
- R 3 is hydrogen; d-C 6 alkyl; or CrC 6 alkoxy;
- R 4 is hydrogen; or C r C 4 alkyl;
- R 5 and R 6 independently from each other are CrC 8 alkyl; n is 0; or 1; and p is a number from 0 to 5.
- the fluoren derivative (a 4 ) is preferably selected from derivatives of cyano(9H-fluoren-9- ylidene)acetic acid, and diesters and polyesters of 9H-fluoren-ylidene malonic acid. These compounds are disclosed in US 2004/0057912.
- component (a 4 ) is used as component (a 4 ) in the present invention.
- naphthalene dicarboxylic acid derivatives (a 5 ) preferably correspond to the formula
- Ri is a radical of formula (4a) k is a number from 1 to 13;
- R 2 is selected from the group consisting of a compound of formula (4a), or Ci-C 22 alkyl.
- compounds of the formula are preferably used as component (a 5 ) in the present invention.
- Dragosine, green tea concentrate and grape seed extract are typical representatives for stabilizers (a 6 ).
- phenolic antioxidants as listed in the Table below are useful stabilizer components (a 7 ) in the present invention:
- the stabilizers disclosed in the following references can advantageously be used in the present composition: US 2004057914; WO 2003039506;DE 10141473; WO 2003020317; WO 2003020224; US 2002197285; EP 1127569; EP 1127568; FR 2801209; FR 2801207; "A new photostabilizer for full spectrum sunscreens", Cosmetics & Toiletries (2000), 115(6), p. 37-45; US 5993789.
- the stabilizer compounds corresponding to components (ai) to (a 7 ) are used as single components or can be used as mixtures in the present composition consisting of two, three, four or even more of the components (ai) to (a 7 ).
- an effective amount of a stabilizer in accordance with the present invention is understood to mean an amount sufficient to produce a noteworthy and significant improvement in the photostability of the UV filter combination dibenzoylmethane derivative (b) and amino-substituted 2-hydroxybenzophenone derivative (c).
- This minimum amount of photostabilizing agent to be employed which can vary depending on the nature of the cos- metically acceptable vehicle used for the composition, can be determined without any difficulty by means of a conventional test for measuring photostability.
- this UV filter is used in the cosmetic or dermatological composition in a concentration range from 1 to 10 % b.w. of the cosmetic composition.
- the 2-hydroxybenzophenone derivative according to component (c) of the cosmetic or dermatological composition preferably corresponds to formula
- Ri and R 2 independently from each other are hydrogen; Ci-C 30 alkyl; C 2 -Ci o alkenyl; C 3 -Ci 0 cycloalkyl; or C 3 -Ci o cycloalkenyl; or
- Ri and R 2 together form, with the nitrogen atom to which they are bonded, a 5- or 6-mem- bered heterocyclic ring member;
- R 3 and R 4 independently from each other, are each CrC 2O alkyl; C 2 -Ci ⁇ alkenyl; C 3 -Ci 0 cyclo- alkyl; C 3 -Ci o cycloalkenyl; C r Ci 2 alkoxy; (d-C 20 )alkoxycarbonyl; C r Ci 2 alkylamino; di(C r Ci 2 )alkylamino; an ar ⁇ l or a heteroaryl radical which is optionally substituted; or a water- solubilizing substituent selected from a carboxylate group, a sulfonate group or an ammonium residue;
- X is hydrogen; -COOR 5 ; or -CONR 6 R 7 ;
- R 5 , R 6 and R 7 independently from each other, are hydrogen; CrC 2O alkyl; C 2 -Ci ⁇ alkenyl; C 3 - Ciocycloalkyl; C 3 -Ci ocycloalkenyl, -(Y 1 O) 0 -Z 1 ; or aryl;
- Y 1 is -(CH 2 J 2 -; -(CH 2 J 3 -; -(CH 2 J 4 -; or -CH-(CH 3 J-CH 2 -; Z 1 is -CH 2 -CH 3 ; -CH 2 -CH 2 CH 3 ; -CH 2 CH 2 -CH 2 -CH 3 or -CH(CH 3 J-CH 3 ; n is an integer from 0 to 3; and o is an integer from 1 to 2.
- CrC 2O alkyl is for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2- methylpropyl, 1,1-dimethyl-ethyl, n-pentyl, 1 -methyl butyl, 2-methyl butyl, 3-methyl-butyl, 2,2- dimethylpropyl, 1 -ethyl propyl, n-hexyl, 1,1-dimethylpropyl, 1,2-di methyl propyl, 1-methyl- pentyl, 2-methyl pentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2- ethylbutyl, 1,2,2-trimethyl
- C 2 -Ci O alkenyl is for example: vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl- 1-butenyl, 2-methyl-2-butenyl, 3-methyl- 1-butenyl, 1-hexenyl, 2- hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.
- Ci-Ci 2 alkoxy is for example methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, 1-methyl- propoxy, 3-methyl butoxy, 2,2-dimethylpropoxy, 1 -methyl- 1 -ethyl propoxy, octoxy, 2-methyl- propoxy, 1,1-dimethylpropoxy, hexoxy, heptoxy or 2-ethylhexoxy.
- C 3 -Ci ocycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclo-propyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentyl- cyclopropyl, 1-methyl-1-butylcyclopropyl, 1,2-dimethylcyclopropyl, 1 -methyl-2-ethylcyclopro- pyl, cyclooctyl, cyclononyl or cyclodecyl.
- C 3 -Ci ocycloalkenyl is for example cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopenta- dienyl, cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, cycloheptenyl, cyclohepta- trienyl, cyclooctenyl, 1,5-cyclooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecenyl.
- the cycloalkyl or cycloalkenyl radicals can comprise one or more substituents (preferably from 1 to 3) and are selected, for example, from halogen, such as chlorine, fluorine or bromine; cyano; nitro; amino; Ci-C 4 alkylamino; di(C r C 4 )alkylamino; d-C 4 alkyl; C r C 4 alkoxy; or hydroxyl. They can also comprise from 1 to 3 heteroatoms, such as sulphur, oxygen or nitrogen, the free valencies of which can be occupied by a hydrogen or a C r C 4 alkyl radical.
- the aryl groups are preferably chosen from phenyl or naphthyl rings which can comprise one or more substituents (preferably from 1 to 3) chosen, for example, from halogen, such as chlorine, fluorine or bromine; cyano; nitro; amino; Ci-C 4 alkylamino; di(Ci-C 4 )alkylamino; d- C 4 alkyl; C r C 4 alkoxy; or hydroxyl. Preference is more particularly given to phenyl, methoxyphenyl and naphthyl.
- the heteroaryl groups generally comprise one or more heteroatoms chosen from sulphur, oxygen or nitrogen.
- the water-solubilizing groups are, for example, carboxylate or sulphonate groups and more particularly their salts with physiologically acceptable cations, such as alkali metal salts or tri- alkylammonium salts, such as tri(hydroxyalkyl)-ammonium or 2-methylpropan-1-ol-2-ammo- nium salts. Mention may also be made of ammonium groups, such as alkylammoniums, and their salified forms with physiologically acceptable anions.
- the amino groups can be attached to the benzene ring in the ortho, meta or para position with respect to the carbonyl radical and more preferably in the para position.
- the 2-hydroxybenzophenone derivative (b) in the cosmetic or dermatological composition corresponds to formula
- Ri and R 2 independently from each other, are hydrogen; or C r C 8 alkyl; or together form, with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocyclic ring member; and R 5 is hydrogen; d-C 5 alkyl; or a C 3 -C 6 cycloalkyl.
- component (b) is used as component (b) in the cosmetic or dermatological composition.
- dibenzoyl methane derivatives according to compnent (b) according to the present invention are products which are already well known per se and which are disclosed in particular in FR 2,326,405, FR 2,440,933 and EP 0,114,607, the teachings of which documents are, insofar as they affect the actual definition of these products, entirely included by way of references in the present description.
- dibenzoylmethane derivatives (b) are: 2-methyldibenzoylmethane; 4-methyl- dibenzoylmethane; 4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane; 2,4-di- methyldibenzoylmethane; 2,5-dimethyldibenzoylmethane; 4,4 1 -diisopropyldibenzoylmethane;
- Another preferred dibenzoylmethane derivative according to the present invention is 4-iso- propyldibenzoylmethane, a screening agent sold under the name of "Eusolex 8020" by Merck and corresponding to the formula
- the dibenzoylmethane derivative (b) isresent in the compositions in accordance with the invention at contents preferably ranging from 0.3 to 10 % by weight and more preferably from 0.5 to n10 % by weight and more particularly from 0.5 to 8 % by weight, with respect to the total weight of the composition.
- the cosmetic or dermatological composition comprising at least
- a stabilizing agent selected from a diphenylacrylate UV filter (ai), a benzylidene cmphor derivative (a 2 ), an organosiloxane comrising benzalemalonate groups (a 3 ), a fluoren derivative (a 4 ), and a naphthalene dicarboxylic acid derivative (a 5 ); 2.0 to 5 % b.w of a dibenzoylmethane derivative (b); and 0.3 to 10 % b.w. of an amino-substituted 2-hydroxybenzophenone derivative (c); is a further object of the present invention.
- a stabilizing agent selected from a diphenylacrylate UV filter (ai), a benzylidene cmphor derivative (a 2 ), an organosiloxane comrising benzalemalonate groups (a 3 ), a fluoren derivative (a 4 ), and a naphthalene dicarboxylic acid derivative (a 5
- compositions according to the present invention comprising components (a), (b) and (c) are particularly suitable as UV filters, i.e. for protecting UV-sen- sitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compositions are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations.
- the cosmetic formulations or dermatological compositions according to the present invention may additionally contain one or more than one further UV filter as listed in Table 1.
- the cosmetic or dermatological preparations can be prepared by physically mixing the UV absorber(s) with the adjuvant using customary methods, for example by simply stirring to ⁇ gether the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, like octyl methoxy cinnamate, salicylic acid isooctyl ester etc..
- the stabilizing agents (ai) - (a 7 ) can also be used for tabilizing the specific amino-substituted 2-hydroxybenzophenone derivative (c). This is another object of the present invention.
- Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight, based on the total weight of the composition, of the UV filter compontents (a), (b) and (c).
- mixing ratios of from 20:80 to 80:20, preferably from 40:60 to 60:40 and most preferably approximately 50:50.
- Such mixtures can be used, inter alia, to improve the solubility or to increase the UV absorption.
- the UV filter compounds (a), (b) and (c) according to the present invention as well as the additional filters listed in Table 1 can be used either in the dissolved state (soluble organic filters, solubelized organic filters) or in the micronised state (nanoscalar organic filters, particulate organic filters, UV-absorber pigments).
- Any known process suitable for the preparation of microparticles can be used for the pre ⁇ paration of the micronised UV absorbers, for example wet-milling, wet-kneading, spray- drying from a suitable solvent, by the expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) of supercritical fluids (e.g.
- milling apparatus for the preparation of the micronised organic UV absorbers there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high ⁇ speed mixing mill.
- the grinding is preferably carried out with a grinding aid.
- kneading apparatus for the preparation of the micronised organic UV absorbers examples are typically sigma-hook batch kneaders but also serial batch kneaders (IKA-Werke) or continuous kneaders (Contiuna from Werner und Pfleiderer).
- Useful low molecular weight grinding aids for the micronizing processes mentioned above are surfactants and emulsifies.
- Useful polymeric grinding aids for water dispersion are cosmetically acceptable water soluble polymers with Mn > 500 g/mol, for example acrylates (Salcare types), modified or non- modified polysaccharides, polyglucosides or xanthan gum. Furthermore an alkylated vinylpyrrolidone polymer, a vi nyl pyrrol idone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or a phospholipid may be used. Oil dispersions may contain cosmetically acceptable waxy polymers or natural waxes as polymeric grinding aid in order to adjust viscosity during and after processing. Examples of other useful polymeric grinding aids are dieclosed below in the chapter "polymers”.
- Useful solvents for the grinding process are water, brine, (poly-)ethylenglycol, glycerine or cosmetically acceptable oils.
- Other useful sovents are disclosed below in the chapters “esters of fatty acids”, “natural and synthetic triglycerides including glyceryl esters and derivatives”, “perlescent waxes”, “hydrocarbon oils” and “silicones or siloxanes”.
- the micronised UV absorbers so obtained usually have an average particle size from 0.02 to 2, preferably from 0.03 to 1.5, and more especially from 0.05 to 1.0 micrometer.
- the UV absorbers used in the cosmetic or dermatological compositions of the present in ⁇ vention can also be used as dry substrates in powder form.
- the UV absor ⁇ bers are subjected to known grinding methods, such as vacuum atomization, countercurrent spray-drying etc.
- UV absorbers used in the cosmetic or dermatological compositions of the present in ⁇ vention can also be used in specific carriers for cosmetics, for example in solid lipid nano- particles (SLN) or in inert sol-gel microcapsules wherein the UV absorbers are encapsulated (Pharmazie, 2001 (56), p. 783-786).
- SSN solid lipid nano- particles
- sol-gel microcapsules wherein the UV absorbers are encapsulated
- the cosmetic or dermatological preparations may be, for example, creams, gels, lotions, al ⁇ coholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments.
- the cosmetic or pharma- ceutical preparations may contain further adjuvants as described below.
- the preparations contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of a UV absorber composition comprising the components (a), (b) and (c), from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil com ⁇ ponent, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of
- the cosmetic or dermatological preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick prepa ⁇ rations, powders or ointments.
- the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.
- water- and oil-containing emulsions e.g.
- the preparations contain, for example, from 0.1 to 30 % by weight, pre ⁇ ferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvants
- the cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds like fatty alcohols, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes, hydrocarbon oils, silicones or siloxanes (organosubstituted polysiloxanes), fluorinated or perfluorinated oils, mulsifiers, super-fatting agents, surfactants, consistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotropic agents, preservatives and bacteria-inhibiting agents, perfume oils, colourants, and polymeric beads or hollow spheres as SPF enhancers.
- additional compounds like fatty alcohols, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes, hydrocarbon oils, silicones or siloxanes (organosubstituted polysiloxanes), fluorin
- Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations:
- skin-care preparations e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes, bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts; - skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g.
- eyeshadow preparations mascara, eyeliner, eye creams or eye-fix creams
- lip-care preparations e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers
- foot-care preparations e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations
- - light-protective preparations such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations
- skin-tanning preparations e.g.
- depigmenting preparations e.g. preparations for bleaching the skin or skin-lightening preparations
- - insect-repellents e.g. insect-repellent oils, lotions, sprays or sticks
- deodorants such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons
- antiperspirants e.g. antiperspirant sticks, creams or roll-ons
- preparations for cleansing and caring for blemished skin e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks
- hair-removal preparations in chemical form (depilation) e.g.
- hair-removing powders liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair- removing preparations in gel form or aerosol foams
- shaving preparations e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions
- fragrance preparations e.g. fragrances (eau de Cologne, eau de toilette, eau de perfume, perfume de toilette, perfume), perfume oils or perfume creams
- cosmetic hair-treatment preparations e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g.
- pretreatment preparations hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair- setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen per- oxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile.
- hair-structuring preparations e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair- setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen per- oxide solutions, lightening shampoos, bleaching cream
- the final formulations listed may exist in a wide variety of presentation forms, for example: in the form of liquid preparations as a VWO, O/W, ONSIIO, W/O/W or PIT emulsion and all kinds of microemulsions, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a powder, a lacquer, a tablet or make-up, in the form of a stick, in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste.
- a spray spray with propellent gas or pump-action spray
- aerosol aerosol
- cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams.
- light-protective preparations such as sun milks, lotions, creams, oils, sunblocks or tropicals
- pretanning preparations or after-sun preparations also skin-tanning preparations, for example self-tanning creams.
- sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray are particularly interested.
- hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair- straightening preparations, liquid hair-setting preparations, hair foams and hairsprays.
- hair-washing preparations in the form of shampoos.
- a shampoo has, for example, the following composition: from 0.01 to 5 % by weight of a UV absorber composition according to the invention comprising the components (a), (b) and (c), 12.0 % by weight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%.
- a UV absorber composition according to the invention comprising the components (a), (b) and (c), 12.0 % by weight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%.
- the cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.
- composition (A) is applied on rough quarz-plates (2 ⁇ l/cm 2 ).
- Solvent B Acetonitrile / THF 9: 1 + 2g/l TBAHS temperature: 35°C wavelength: 354nm (for Detection of the compound of formula (101))
Abstract
Diclosed is the use of an effective photo-stabilizing amount of stabilizing agent (a) selected from a diphenylacrylate UV filter (a1), a benzylidene amphor derivative (a2), an organosiloxane comrising benzalemalonate groups (a3), a fluoren derivative (a4), and a naphthalene dicarboxylic acid derivative (a5) for improving the stability with respect to UV radiation of a cosmetic or dermatological composition comprising a UV filter combination of at least one dibenzoylmethane derivative (b) and of at least one specific amino-substituted 2-hydroxybenzophenone derivative (c).
Description
Photo-stable cosmetic or dermatological compositions
The present invention relates to the use of a specific stabilizing agent (a) for improving the stability with respect to UV radiation of a cosmetic or dermatological composition comprising a UV filter combination of at least one dibenzoylmethane derivative (b) and of at least one specific amino-substituted 2-hydroxybenzophenone derivative (c).
It has long been known that prolonged exposure to UV radiation can lead to the formation of erythemas or light dermatoses, as well as to an increased incidence of skin cancers or accelerated skin ageing.
Various sunscreen formulations have been proposed which include materials which are in¬ tended to counteract UV radiation, thereby inhibiting the said undesired effects on the skin.
A great number of compounds have been proposed for use as UV protectants in sunscreen formulations.
In this respect, a particular advantageous family of UV-A screening agents is currently com¬ posed of dibenzoylmethane derivatives and in particular 4-tert-butyl-4'-methoxydibenzoyl- methane; this is because these derivatives exhibit a high intrinsic absorbance. Dibenzoyl- methane derivatives are well known per se as screening agents actives in the UV-A region, and are disclosed in particular in FR-A-2 326 405, FR-A-2 440 933 and EP-A-O 114 607. Furthermore, 4-tert-butyl-4'-methoxydibenzoylmethane is currently offered for sale under the trademark of "Parsol 1789" by DSM.
Unfortunately, it is found that dibenzoylmethane derivatives are relatively sensitive to UV radiation (in particular UV-A radiation), AND more specifically, that they have an unfortunate tendency to more or less rapid decomposition under the effect of the latter. Thus, this substantial lack of photochemical stability of dibenzoylmethane derivatives with respect to UV radiation does not make it possible to guarantee constant protection during prolonged exposure to the sun, so that repeated sun screen applications at regular and frequent intervals have to be carried out by the user in order to obtain effective protection of the skin against UV radiation.
The photostabilization of dibenzoylmethane derivatives with respect to UV radiation con¬ stitutes a problem, which has not yet been solved until now in a completely satisfactory manner.
In US 6,699,461 it is is suggested to improve the photochemical stability of dibenzoyl¬ methane derivatives containing cosmetic or dermatological compositions with specific amino- substituted 2-hydroxybenzophenone derivatives. These compositions do not comprise p-methyl benzyl idenecamphor.
Unfortunately, the addition of a 2-hydroxybenzophenone derivative in cosmetic or derma¬ tological compositions photo-stabilizes the dibenzoylmethane derivative but simultaneously destabilizes the 2-hydroxybenzophenone derivative.
Surprisingly it was found, that the addition of specific amounts of a specific stabilizing agent will significantly improve the photostability of cosmetic or dermatological compositions com¬ prising the combination of 2-hydroxybenzophenone and dibenzoylmethane derivatives.
Therefore, the present invention relates to the use of an effective photo-stabilizing amount of stabilizing agent (a) selected from a diphenylacrylate UV filter (ai), a benzyl idene camphor derivative (a2), an organosiloxane comrising benzalemalonate groups (a3), a fluoren derivative (a4), a naphthalene dicarboxylic acid derivative (a5) a natural occurring stabilizer (a6); and a phenolic antioxidant (a7); for improving the stability with respect to UV radiation of a cosmetic or dermatological com¬ position comprising a UV filter combination of at least one dibenzoylmethane derivative (b) and of at least one specific amino-substituted 2-hydroxybenzophenone derivative (c).
The diphenylacrylate UV filter (ai) which is used in the present invention for the stabilization of cosmetic or dermatological composition is preferably selected from 2-ethylhexyl 2-
cyano,3,3-diphenylacrylate which corresponds to the
formula (1) (Octocrylene).
Suitable benzylidene camphor derivatives (a2) are disclosed in US-A-5,605,680.
Preferably, p-methylbenzylidene camphor is used in the present invention as component (a2).
The organosiloxane comprising benzalemalonate groups (a3) preferably correspond to the formula
(2b) , wherein
R is CrCiOalkyl; phenyl; or 3,3,3-trifluoropropyl, at least 80% of the number of the R radicals being methyl radicals; r is an integer rom O to 200; s is an integer rom 0 to 50 u is an integer from 1 to 20; t is an integer from 0 to 20; wherein t + u is equal to or greater than 3; and. A and/or B is a benzalmalonate radical.
A is preferably the radical of formula (2c) X.5 , wherein
Ri and R2 are each hydrogen; OH; trimethylsiloxy; CrC6alkyl; CrC6alkoxy; or a radical of the
H formula (2d) -(O)-(CH2)p-C-CH2- ;
R4 with the proviso that one of the radicals Ri and R2 is the bivalent radical of formula (2d); R3 is hydrogen; d-C6alkyl; or CrC6alkoxy; R4 is hydrogen; or CrC4alkyl; and
R5 and R6, independently from each other are CrC8alkyl; n is 0; or 1; and p is a number from 0 to 5.
The fluoren derivative (a4) is preferably selected from derivatives of cyano(9H-fluoren-9- ylidene)acetic acid, and diesters and polyesters of 9H-fluoren-ylidene malonic acid. These compounds are disclosed in US 2004/0057912.
Preferably, a 9-methylene-9H-fluoren derivative of formula
is used as component (a4) in the present invention.
The naphthalene dicarboxylic acid derivatives (a5) preferably correspond to the formula
(4) R1O9C-(K ^T H — C09R9 • wherein
Ri is a radical of formula (4a)
k is a number from 1 to 13; and
R2 is selected from the group consisting of a compound of formula (4a), or Ci-C22alkyl.
The compounds are disclosed in WO 01/087528.
Preferably, compounds of the formula
are preferably used as component (a5) in the present invention.
Dragosine, green tea concentrate and grape seed extract. are typical representatives for stabilizers (a6).
The phenolic antioxidants as listed in the Table below are useful stabilizer components (a7) in the present invention:
Furthermore, the stabilizers disclosed in the following references, can advantageously be used in the present composition: US 2004057914; WO 2003039506;DE 10141473; WO 2003020317; WO 2003020224; US 2002197285; EP 1127569; EP 1127568; FR 2801209; FR 2801207; "A new photostabilizer for full spectrum sunscreens", Cosmetics & Toiletries (2000), 115(6), p. 37-45; US 5993789.
The stabilizer compounds corresponding to components (ai) to (a7) are used as single components or can be used as mixtures in the present composition consisting of two, three, four or even more of the components (ai) to (a7).
The term "effective amount of a stabilizer " in accordance with the present invention is understood to mean an amount sufficient to produce a noteworthy and significant improvement in the photostability of the UV filter combination dibenzoylmethane derivative (b) and amino-substituted 2-hydroxybenzophenone derivative (c). This minimum amount of photostabilizing agent to be employed, which can vary depending on the nature of the cos- metically acceptable vehicle used for the composition, can be determined without any difficulty by means of a conventional test for measuring photostability.
Preferably, this UV filter is used in the cosmetic or dermatological composition in a concentration range from 1 to 10 % b.w. of the cosmetic composition.
The 2-hydroxybenzophenone derivative according to component (c) of the cosmetic or dermatological composition preferably corresponds to formula
(5) wherein
Ri and R2, independently from each other are hydrogen; Ci-C30alkyl; C2-Ci oalkenyl; C3-Ci0 cycloalkyl; or C3-Ci ocycloalkenyl; or
Ri and R2 together form, with the nitrogen atom to which they are bonded, a 5- or 6-mem- bered heterocyclic ring member;
R3 and R4, independently from each other, are each CrC2Oalkyl; C2-Ciθalkenyl; C3-Ci0cyclo- alkyl; C3-Ci ocycloalkenyl; CrCi2alkoxy; (d-C20)alkoxycarbonyl; CrCi2alkylamino; di(Cr Ci2)alkylamino; an arγl or a heteroaryl radical which is optionally substituted; or a water- solubilizing substituent selected from a carboxylate group, a sulfonate group or an ammonium residue;
X is hydrogen; -COOR5; or -CONR6R7;
R5, R6 and R7, independently from each other, are hydrogen; CrC2Oalkyl; C2-Ciθalkenyl; C3- Ciocycloalkyl; C3-Ci ocycloalkenyl, -(Y1O)0-Z1; or aryl;
Y1 is -(CH2J2-; -(CH2J3-; -(CH2J4-; or -CH-(CH3J-CH2-;
Z1 is -CH2-CH3; -CH2-CH2CH3; -CH2CH2-CH2-CH3 or -CH(CH3J-CH3; n is an integer from 0 to 3; and o is an integer from 1 to 2.
CrC2Oalkyl is for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2- methylpropyl, 1,1-dimethyl-ethyl, n-pentyl, 1 -methyl butyl, 2-methyl butyl, 3-methyl-butyl, 2,2- dimethylpropyl, 1 -ethyl propyl, n-hexyl, 1,1-dimethylpropyl, 1,2-di methyl propyl, 1-methyl- pentyl, 2-methyl pentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2- ethylbutyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1 -ethyl-2-methyl propyl, n-heptyl, n- octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n- hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-icosyl.
C2-CiOalkenyl is for example: vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl- 1-butenyl, 2-methyl-2-butenyl, 3-methyl- 1-butenyl, 1-hexenyl, 2- hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.
Ci-Ci2alkoxy is for example methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, 1-methyl- propoxy, 3-methyl butoxy, 2,2-dimethylpropoxy, 1 -methyl- 1 -ethyl propoxy, octoxy, 2-methyl- propoxy, 1,1-dimethylpropoxy, hexoxy, heptoxy or 2-ethylhexoxy.
C3-Ci ocycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclo-propyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentyl- cyclopropyl, 1-methyl-1-butylcyclopropyl, 1,2-dimethylcyclopropyl, 1 -methyl-2-ethylcyclopro- pyl, cyclooctyl, cyclononyl or cyclodecyl.
C3-Ci ocycloalkenyl is for example cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopenta- dienyl, cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, cycloheptenyl, cyclohepta- trienyl, cyclooctenyl, 1,5-cyclooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecenyl.
The cycloalkyl or cycloalkenyl radicals can comprise one or more substituents (preferably from 1 to 3) and are selected, for example, from halogen, such as chlorine, fluorine or bromine; cyano; nitro; amino; Ci-C4alkylamino; di(CrC4)alkylamino; d-C4alkyl; CrC4alkoxy;
or hydroxyl. They can also comprise from 1 to 3 heteroatoms, such as sulphur, oxygen or nitrogen, the free valencies of which can be occupied by a hydrogen or a CrC4alkyl radical.
The aryl groups are preferably chosen from phenyl or naphthyl rings which can comprise one or more substituents (preferably from 1 to 3) chosen, for example, from halogen, such as chlorine, fluorine or bromine; cyano; nitro; amino; Ci-C4alkylamino; di(Ci-C4)alkylamino; d- C4alkyl; CrC4alkoxy; or hydroxyl. Preference is more particularly given to phenyl, methoxyphenyl and naphthyl.
The heteroaryl groups generally comprise one or more heteroatoms chosen from sulphur, oxygen or nitrogen.
The water-solubilizing groups are, for example, carboxylate or sulphonate groups and more particularly their salts with physiologically acceptable cations, such as alkali metal salts or tri- alkylammonium salts, such as tri(hydroxyalkyl)-ammonium or 2-methylpropan-1-ol-2-ammo- nium salts. Mention may also be made of ammonium groups, such as alkylammoniums, and their salified forms with physiologically acceptable anions.
Mention may in particular be made, as examples of the 5- or 6-membered heterocyclic ring member; formed by the Riand R2 with the nitrogen atom, of pyrrolidine or piperidine.
The amino groups can be attached to the benzene ring in the ortho, meta or para position with respect to the carbonyl radical and more preferably in the para position.
Preferably, the 2-hydroxybenzophenone derivative (b) in the cosmetic or dermatological composition corresponds to formula
(6) wherein
Ri and R2, independently from each other, are hydrogen; or CrC8alkyl; or together form, with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocyclic ring member; and
R5 is hydrogen; d-C5alkyl; or a C3-C6cycloalkyl.
Most preferably the compound of formula
is used as component (b) in the cosmetic or dermatological composition.
The dibenzoyl methane derivatives according to compnent (b) according to the present invention are products which are already well known per se and which are disclosed in particular in FR 2,326,405, FR 2,440,933 and EP 0,114,607, the teachings of which documents are, insofar as they affect the actual definition of these products, entirely included by way of references in the present description.
According to the present invention, it is possible, of course, to employ one or more dibenzoyl- methane derivatives.
Examples of dibenzoylmethane derivatives (b) are: 2-methyldibenzoylmethane; 4-methyl- dibenzoylmethane; 4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane; 2,4-di- methyldibenzoylmethane; 2,5-dimethyldibenzoylmethane; 4,41-diisopropyldibenzoylmethane;
4,4'-dimethoxydibenzoylmethane; 4-tert-butyl-4'-methoxydibenzoylmethane; 2-methyl-5-iso- propyl-4'-methoxydibenzoyl methane; 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane;
2,4-dimethyl-41-methoxydibenzoylmethane; or 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoyl- methane.
Preference is very particularly given according to the present invention, among the above- mentioned dibenzoylmethane derivatives, to the use of 4-tert-butyl-4'-methoxydibenzoyl- methane, in particular that offered for sale under the trademark of "Parsol 1789" by Hoff- mann-LaRoche, this screening agent corresponding to the following formula
Another preferred dibenzoylmethane derivative according to the present invention is 4-iso- propyldibenzoylmethane, a screening agent sold under the name of "Eusolex 8020" by Merck and corresponding to the formula
(9) ; or 4-Ethylhexyl-4'Methoxydibenzoylmethane
corresponding to formula
The dibenzoylmethane derivative (b) isresent in the compositions in accordance with the invention at contents preferably ranging from 0.3 to 10 % by weight and more preferably from 0.5 to n10 % by weight and more particularly from 0.5 to 8 % by weight, with respect to the total weight of the composition.
The cosmetic or dermatological composition comprising at least
1 to 10 % b.w of a stabilizing agent (a) selected from a diphenylacrylate UV filter (ai), a benzylidene cmphor derivative (a2), an organosiloxane comrising benzalemalonate groups (a3), a fluoren derivative (a4), and a naphthalene dicarboxylic acid derivative (a5); 2.0 to 5 % b.w of a dibenzoylmethane derivative (b); and 0.3 to 10 % b.w. of an amino-substituted 2-hydroxybenzophenone derivative (c); is a further object of the present invention.
The cosmetic or dermatological compositions according to the present invention comprising components (a), (b) and (c) are particularly suitable as UV filters, i.e. for protecting UV-sen- sitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compositions are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations.
The cosmetic formulations or dermatological compositions according to the present invention may additionally contain one or more than one further UV filter as listed in Table 1.
The cosmetic or dermatological preparations can be prepared by physically mixing the UV absorber(s) with the adjuvant using customary methods, for example by simply stirring to¬ gether the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, like octyl methoxy cinnamate, salicylic acid isooctyl ester etc..
The stabilizing agents (ai) - (a7) can also be used for tabilizing the specific amino-substituted 2-hydroxybenzophenone derivative (c). This is another object of the present invention.
Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight, based on the total weight of the composition, of the UV filter compontents (a), (b) and (c).
Preference is given to the use of mixing ratios of the UV filter components (a), (b) and (c) according to the present invention and optionally further light-protective agents (as described in Table 2) from 1 :99 to 99:1, preferably from 1 :95 to 95:1 and most preferably from 10:90 to 90:10, based on weight. Of special interest are mixing ratios of from 20:80 to 80:20, preferably from 40:60 to 60:40 and most preferably approximately 50:50. Such mixtures can be used, inter alia, to improve the solubility or to increase the UV absorption.
The UV filter compounds (a), (b) and (c) according to the present invention as well as the additional filters listed in Table 1 can be used either in the dissolved state (soluble organic filters, solubelized organic filters) or in the micronised state (nanoscalar organic filters, particulate organic filters, UV-absorber pigments).
Any known process suitable for the preparation of microparticles can be used for the pre¬ paration of the micronised UV absorbers, for example wet-milling, wet-kneading, spray- drying from a suitable solvent, by the expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) of supercritical fluids (e.g. CO2) in which the UV filter or filters is/are dissolved, by reprecipitation from suitable solvents, including supercritical fluids (GASR process = Gas Anti-Solvent Recrystallisation / PCA process = Precipitation with Compressed Anti-solvents).
As milling apparatus for the preparation of the micronised organic UV absorbers there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high¬ speed mixing mill. The grinding is preferably carried out with a grinding aid. As kneading apparatus for the preparation of the micronised organic UV absorbers examples are typically sigma-hook batch kneaders but also serial batch kneaders (IKA-Werke) or continuous kneaders (Contiuna from Werner und Pfleiderer).
Useful low molecular weight grinding aids for the micronizing processes mentioned above are surfactants and emulsifies.
Useful polymeric grinding aids for water dispersion are cosmetically acceptable water soluble polymers with Mn > 500 g/mol, for example acrylates (Salcare types), modified or non- modified polysaccharides, polyglucosides or xanthan gum. Furthermore an alkylated vinylpyrrolidone polymer, a vi nyl pyrrol idone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or a phospholipid may be used. Oil dispersions may contain cosmetically acceptable waxy polymers or natural waxes as polymeric grinding aid in order to adjust viscosity during and after processing. Examples of other useful polymeric grinding aids are dieclosed below in the chapter "polymers".
Useful solvents for the grinding process are water, brine, (poly-)ethylenglycol, glycerine or cosmetically acceptable oils. Other useful sovents are disclosed below in the chapters "esters of fatty acids", "natural and synthetic triglycerides including glyceryl esters and derivatives", "perlescent waxes", "hydrocarbon oils" and "silicones or siloxanes".
The micronised UV absorbers so obtained usually have an average particle size from 0.02 to 2, preferably from 0.03 to 1.5, and more especially from 0.05 to 1.0 micrometer.
The UV absorbers used in the cosmetic or dermatological compositions of the present in¬ vention can also be used as dry substrates in powder form. For that purpose the UV absor¬ bers are subjected to known grinding methods, such as vacuum atomization, countercurrent spray-drying etc.
The UV absorbers used in the cosmetic or dermatological compositions of the present in¬ vention can also be used in specific carriers for cosmetics, for example in solid lipid nano- particles (SLN) or in inert sol-gel microcapsules wherein the UV absorbers are encapsulated (Pharmazie, 2001 (56), p. 783-786).
The cosmetic or dermatological preparations may be, for example, creams, gels, lotions, al¬ coholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above-mentioned UV filters, the cosmetic or pharma- ceutical preparations may contain further adjuvants as described below.
As water- and oil-containing emulsions (e.g. VWO, O/W, 0/W/O and W/O/W emulsions or mi- croemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of a UV absorber composition comprising the components (a), (b) and (c), from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil com¬ ponent, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvants.
The cosmetic or dermatological preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick prepa¬ rations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.
As water- and oil-containing emulsions (e.g. W/O, C7W, ONSIIO and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, pre¬ ferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvants.
The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds like fatty alcohols, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes, hydrocarbon oils, silicones or siloxanes (organosubstituted polysiloxanes), fluorinated or perfluorinated oils, mulsifiers, super-fatting agents, surfactants, consistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotropic agents, preservatives and bacteria-inhibiting agents, perfume oils, colourants, and polymeric beads or hollow spheres as SPF enhancers.
Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations:
skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes, bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts; - skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care
preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations; - light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; skin-tanning preparations, e.g. self-tanning creams; depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations; - insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks; deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons; antiperspirants, e.g. antiperspirant sticks, creams or roll-ons; preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks; hair-removal preparations in chemical form (depilation), e.g. hair-removing powders, liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair- removing preparations in gel form or aerosol foams; shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions; fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams; cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair- setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen per- oxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile.
The final formulations listed may exist in a wide variety of presentation forms, for example:
in the form of liquid preparations as a VWO, O/W, ONSIIO, W/O/W or PIT emulsion and all kinds of microemulsions, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a powder, a lacquer, a tablet or make-up, in the form of a stick, in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste.
Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.
Of special importance as cosmetic preparations for the hair are the above-mentioned prepa¬ rations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair- straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.
A shampoo has, for example, the following composition: from 0.01 to 5 % by weight of a UV absorber composition according to the invention comprising the components (a), (b) and (c), 12.0 % by weight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%.
Light/dry cosmetic oils Ingredients 1 2 3 4
The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.
Examples
Preparation of the samples for the determination of the photostability
2% of the compound of formula (101)
(Uvinul A Plus),
5% of the compound of formula (102) (Octocrylene) and
3 % of the compound of formula (103) (Parsol 1789)
are dissolved in a cosmetic carrier.
This composition (A) is applied on rough quarz-plates (2 μl/cm2).
The times of irradiation are
- Oh (no irradiation), - 1h (5 MED), - 2h (10 MED),
- 4h (20 MED) and
- 1Oh (50 MED) with an Altas CPS+ sunlight simulator. For sufficient statistics 8 plates per time (x MED) are prepared. After irradiation, the samples can be recovered completely with a defined amount (5 ml) of a solvent (tetrahydrofurane).
HPLC:
The recovery of the UV-absorber was analyzed via HPLC:
column: Hypersil ODS 5μm, 250mm x 4mm Solvent A: Water + 2g/l TBAHS
Solvent B: Acetonitrile / THF 9: 1 + 2g/l TBAHS temperature: 35°C wavelength: 354nm (for Detection of the compound of formula (101))
For comparison, the experiment is carried out in the same manner, but with a preparation comprising only
2 % of the compound of formula (101) and
3 % of the compound of formula (103) without the compound of formula (102) (= B).
The results: are listed in Table 2:
The results in Table 2 clearly demonstrate that the addition of the diphenylacrylate UV absorber of formula (102) (= Octocrylene) stabilizes the 2-hydroxybenzophenone UV ab¬ sorber of formula (101) (= Uvinul A Plus) in a UV absorber composition which additionally comprises a UV absorber of formula (103 (= Parsol 1789; Avobenzone)
Claims
1. Use of an effective photo-stabilizing amount of a stabilizing agent (a) selected from a diphenylacrylate UV filter (ai), a benzylidene camphor derivative (a2), an organosiloxane comrising benzalemalonate groups (a3), a fluoren derivative (a4), a naphthalene dicarboxylic acid derivative (a5) a natural occurring stabilizer (a6); and a phenolic antioxidant (a7); for improving the stability with respect to UV radiation of a cosmetic or dermatological composition comprising a UV filter combination of at least one dibenzoylmethane derivative
(b) and of at least one specific amino-substituted 2-hydroxybenzophenone derivative (c).
2. Use according to claim 1 wherein the diphenylacrylate UV filter (ai) is 2-ethylhexyl 2- cyano,3,3-diphenylacrylate of formula
3. Use according to claim 1 , wherein the benzylidene cmphor derivative (a2) is p- methylbenzylidene camphor.
4. Use according to claim 1 , wherein the organosiloxane comprising benzalemalonate groups (a3) corresponds to the formula
(2b) Si-O- -Si-O- , wherein R A
R is CrCiOalkyl; phenyl; or 3,3,3-trifluorpopropyl, at least 80% of the number of the R radicals being methyl radicals; r is an integer rom 0 to 200; s is an integer rom 0 to 50 u is an integer from 1 to 20; t is an integer from 0 to 20; wherein t + u is equal to or greater than 3; and. A and/or B is a benzalmalonate radical.
5. Use according to claim 1 , wherein the fluorein derivative (a4) is selected from derivatives of cyano(9H-fluoren-9-ylidene)acetic acid, and diesters and polyesters of 9H-fluoren- ylidenemalonic acid.
6. Use according to claim 1, wherein the naphthalene dicarboxylic acid derivative (a5) corresponds to the formula
(4) . wherein
Ri is a radical of formula (4a)
k is 1 to 13; and
R2 is selected from the group consisting of a compound of formula (4a), or CrC22alkyl.
7. Use according to claim 1 , wherein the natural occurring stabilizer (a6) is selected from dragosine, green tea concentrate and grape seed extract.
8. Use according to any of claims 1 to 7, wherein the stabilizing agent (a) is used in a concentration from 1 to 10 % b.w. of the cosmetic or dermatological composition.
9. Use according to any of claims 1 to 8, wherein the dibenzoylmethane derivative (b) is 4- tert-butyl-4'-methoxydibenzoyl methane.
10. Use according to any of claims 1 to 9, wherein the 2-hydroxybenzophenone derivative (c) corresponds to formula
(5) wherein
Ri and R2, independently from each other are hydrogen; Ci-C30alkyl; C2-Ci oalkenyl; C3-Ci0 cycloalkyl; or C3-Ci ocycloalkenyl; or Ri and R2 together form, with the nitrogen atom to which they are bonded, a 5- or 6-mem- bered heterocyclic ring member;
R3 and R4, independently from each other, are each CrC2Oalkyl; C2-Ciθalkenyl; C3-Ci0cyclo- alkyl; C3-Ci ocycloalkenyl; CrCi2alkoxy; (CrC20)alkoxycarbonyl; Ci-Ci2alkylamino; di(Cr
Ci2)alkylamino; an aryl or a heteroaryl radical which is optionally substituted; or a water- solubilizing substituent selected from a carboxylate group, a sulfonate group or an ammonium residue;
X is hydrogen; -COOR5; or -CONR6R7; R5, R6 and R7, independently from each other, are hydrogen; CrC2Oalkyl; C2-Ciθalkenyl; C3-
Ci0cycloalkyl; C3-Ci ocycloalkenyl, -(Y1O)0-Z1; or aryl; Y1 is -(CH2J2-; -(CH2J3-; -(CH2J4-; or -CH-(CH3J-CH2-;
Z1 is -CH2-CH3; -CH2-CH2CH3; -CH2CH2-CH2-CH3 or -CH(CH3J-CH3; n is an integer from 0 to 3; and o is an integer from 1 to 2.
11. Use according to claim 10, wherein the 2-hydroxybenzophenone derivative (c) corresponds to formula
(6) wherein
Ri and R2, independently from each other, are hydrogen; or d-C8alkyl; or together form, with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocyclic ring member; and
R5 is hydrogen; CrC5alkyl; or a C3-C6cycloalkyl.
12. Use according to claim 10 or 1 1 , wherein the 2-hydroxybenzophenone derivative (c) corresponds to formula
13. Use according to any of claims 1 to 12, wherein the cosmetic or dermatological composition comprises at least
1.0 to 10 % of a stabilizing agent (a) as defined in claim 1 ,
2.0 to 5 % b.w of a di benzoyl methane derivative (b); and
0.3 to 10 % b.w. of an amino-substituted 2-hydroxybenzophenone derivative (c).
14. Cosmetic or dermatological composition comprising at least 1.0 to 10 % of a stabilizing agent (a) as defined in claim 1 ;
2.0 to 5 % b.w of a dibenzoylmethane derivative UV filter (b); and 0.3 to 10 % b.w. of an amino-substituted 2-hydroxybenzophenone derivative UV filter (c).
15. Use of the dabilzers (ai) - (a7) for the stabilization of specific amino-substituted 2- hydroxybenzophenone derivative (c).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05786945.5A EP1793798B1 (en) | 2004-09-29 | 2005-09-19 | Photo-stable cosmetic or dermatological compositions |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04104739 | 2004-09-29 | ||
| EP04106828 | 2004-12-22 | ||
| EP05786945.5A EP1793798B1 (en) | 2004-09-29 | 2005-09-19 | Photo-stable cosmetic or dermatological compositions |
| PCT/EP2005/054641 WO2006034968A1 (en) | 2004-09-29 | 2005-09-19 | Photo-stable cosmetic or dermatological compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1793798A1 true EP1793798A1 (en) | 2007-06-13 |
| EP1793798B1 EP1793798B1 (en) | 2016-04-20 |
Family
ID=35457191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP05786945.5A Active EP1793798B1 (en) | 2004-09-29 | 2005-09-19 | Photo-stable cosmetic or dermatological compositions |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US8119107B2 (en) |
| EP (1) | EP1793798B1 (en) |
| JP (1) | JP5384826B2 (en) |
| KR (1) | KR101269995B1 (en) |
| CN (1) | CN101031277B (en) |
| AU (1) | AU2005288930B2 (en) |
| BR (1) | BRPI0516174B1 (en) |
| ES (1) | ES2582485T3 (en) |
| MX (1) | MX2007003356A (en) |
| WO (1) | WO2006034968A1 (en) |
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|---|---|---|---|---|
| JP5072624B2 (en) * | 2008-01-30 | 2012-11-14 | ポーラ化成工業株式会社 | Cosmetics for nails |
| CN102791248B (en) * | 2009-01-29 | 2016-01-06 | 巴斯夫欧洲公司 | Stablizing of cosmetic composition |
| EP2451427B1 (en) * | 2009-07-07 | 2018-04-25 | Basf Se | Uv filter combinations comprising benzylidene malonates |
| ES2592958T3 (en) * | 2010-02-03 | 2016-12-02 | Unilever N.V. | Composition of photostable sunscreen |
| US8394755B2 (en) | 2010-11-15 | 2013-03-12 | Johnson & Johnson Consumer Companies, Inc. | Polyglyceryl compounds and compositions |
| US9089536B2 (en) | 2012-06-06 | 2015-07-28 | Brian J. Smith | Ophthalmic solution for absorbing ultraviolet radiation and method for absorbing ultraviolet radiation |
| US9145383B2 (en) | 2012-08-10 | 2015-09-29 | Hallstar Innovations Corp. | Compositions, apparatus, systems, and methods for resolving electronic excited states |
| WO2014025370A1 (en) * | 2012-08-10 | 2014-02-13 | Hallstar Innovations Corp. | Tricyclic energy quencher compounds for reducing singlet oxygen generation |
| EP2882824A4 (en) * | 2012-08-10 | 2016-02-24 | Hallstar Innovations Corp | Compositions, apparatus, systems, and methods for resolving electronic excited states |
| US9125829B2 (en) | 2012-08-17 | 2015-09-08 | Hallstar Innovations Corp. | Method of photostabilizing UV absorbers, particularly dibenzyolmethane derivatives, e.g., Avobenzone, with cyano-containing fused tricyclic compounds |
| CA3104441A1 (en) * | 2018-06-18 | 2019-12-26 | Elc Management Llc | Photostabilizing compounds, compositions, and methods |
| US11655215B2 (en) | 2018-06-18 | 2023-05-23 | Elc Management Llc | Photostabilizing compounds, compositions, and methods |
| WO2019245878A1 (en) | 2018-06-18 | 2019-12-26 | Elc Management Llc | Photostabilizing compounds, compositions, and methods |
| JP2022525309A (en) | 2019-03-15 | 2022-05-12 | ビーエーエスエフ ソシエタス・ヨーロピア | Sunscreen composition containing butylmethoxydibenzoylmethane, triazine derivative and light stabilizer |
| JP2023508194A (en) * | 2019-12-25 | 2023-03-01 | ロレアル | Composition for conditioning keratin fibers |
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|---|---|---|---|---|
| LU86703A1 (en) * | 1986-12-08 | 1988-07-14 | Oreal | PHOTOSTABLE COSMETIC COMPOSITION CONTAINING A UV-A FILTER AND A UV-B FILTER, ITS USE FOR PROTECTING THE SKIN AGAINST UV RAYS AND A METHOD OF STABILIZING THE UV-A FILTER WITH THE UV-B FILTER |
| FR2658075B1 (en) * | 1990-02-14 | 1992-05-07 | Oreal | PHOTOSTABLE FILTERING COSMETIC COMPOSITION CONTAINING A UV-A FILTER AND A BETA, BETA-DIPHENYLACRYLATE OR ALPHA-CYANO-BETA, BETA-DIPHENYLACRYLATE. |
| US5306486A (en) * | 1993-03-01 | 1994-04-26 | Elizabeth Arden Co., Division Of Conopco, Inc. | Cosmetic sunscreen composition containing green tea and a sunscreen |
| JP4150501B2 (en) * | 1997-12-24 | 2008-09-17 | シャクリー コーポレイション | Composition with high efficiency skin protection from the damaging effects of ultraviolet light |
| EP1129695A1 (en) | 2000-02-29 | 2001-09-05 | Basf Aktiengesellschaft | Cosmetic or dermatological sunscreen formulations |
| GB0102813D0 (en) * | 2001-02-05 | 2001-03-21 | Nokia Mobile Phones Ltd | Exchange of information in Bluetooth |
| DE10155957A1 (en) | 2001-11-09 | 2003-05-22 | Beiersdorf Ag | Cosmetic and dermatological light protection formulations containing hydroxybenzophenones and pentasodium ethylenediaminetetramethylene phosphonate |
| DE10155965A1 (en) * | 2001-11-09 | 2003-05-22 | Beiersdorf Ag | Cosmetic and dermatological light protection formulations containing hydroxybenzophenones and iminodisuccinic acid and / or their salts |
| DE10155958A1 (en) * | 2001-11-09 | 2003-05-22 | Beiersdorf Ag | Cosmetic and dermatological light protection formulations containing hydroxybenzophenones and alkyl naphthalates |
| DE10155865A1 (en) * | 2001-11-14 | 2003-05-28 | Beiersdorf Ag | UV-protective cosmetic or dermatological composition contains an inorganic micropigment, e.g. titanium oxide, a hydroxybenzophenone and a siloxane elastomer |
| DE10157489A1 (en) * | 2001-11-23 | 2003-06-12 | Beiersdorf Ag | Cosmetic or dermatological composition for protection against ultraviolet radiation comprises a hydroxy benzophenone and a coated silicone elastomer powder |
| FR2833168B1 (en) | 2001-12-07 | 2004-08-27 | Oreal | FILTERING COMPOSITION CONTAINING A FILTER OF THE DIBENZOYLMETHANE DERIVATIVE TYPE AND AN AMINOSUBSTITUTED 2-HYDROXYBENZOPHENONE DERIVATIVE |
| JP2005513093A (en) * | 2001-12-20 | 2005-05-12 | バイヤースドルフ・アクチエンゲゼルシヤフト | Cosmetic and dermatological light-protection formulations comprising hydroxybenzophenones and benzoxazole derivatives |
| US6899866B2 (en) * | 2002-09-06 | 2005-05-31 | Cph Innovations Corporation | Photostabilization of a sunscreen composition with a combination of an α-cyano-β, β-diphenylacrylate compound and a dialkyl naphithalate |
| US6926887B2 (en) * | 2002-09-17 | 2005-08-09 | The C.P. Hall Company | Photostabilizers, UV absorbers, and methods of photostabilizing a sunscreen composition |
| JP2006514661A (en) * | 2003-02-03 | 2006-05-11 | デーエスエム アイピー アセッツ ベー． ヴェー． | Novel stabilized cinnamate sunscreen composition |
-
2005
- 2005-09-19 CN CN200580032986XA patent/CN101031277B/en active Active
- 2005-09-19 WO PCT/EP2005/054641 patent/WO2006034968A1/en active Application Filing
- 2005-09-19 JP JP2007534002A patent/JP5384826B2/en active Active
- 2005-09-19 AU AU2005288930A patent/AU2005288930B2/en active Active
- 2005-09-19 BR BRPI0516174-6A patent/BRPI0516174B1/en active IP Right Grant
- 2005-09-19 ES ES05786945.5T patent/ES2582485T3/en active Active
- 2005-09-19 MX MX2007003356A patent/MX2007003356A/en active IP Right Grant
- 2005-09-19 EP EP05786945.5A patent/EP1793798B1/en active Active
- 2005-09-19 US US11/663,610 patent/US8119107B2/en active Active
- 2005-09-19 KR KR1020077006609A patent/KR101269995B1/en active IP Right Grant
-
2012
- 2012-01-19 US US13/353,507 patent/US20120121524A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2006034968A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008514672A (en) | 2008-05-08 |
| CN101031277A (en) | 2007-09-05 |
| CN101031277B (en) | 2012-12-05 |
| BRPI0516174A (en) | 2008-08-26 |
| ES2582485T3 (en) | 2016-09-13 |
| US8119107B2 (en) | 2012-02-21 |
| AU2005288930A1 (en) | 2006-04-06 |
| US20120121524A1 (en) | 2012-05-17 |
| WO2006034968A1 (en) | 2006-04-06 |
| AU2005288930B2 (en) | 2011-06-23 |
| BRPI0516174B1 (en) | 2015-06-16 |
| US20100143272A1 (en) | 2010-06-10 |
| MX2007003356A (en) | 2008-03-05 |
| KR20070058518A (en) | 2007-06-08 |
| KR101269995B1 (en) | 2013-05-31 |
| JP5384826B2 (en) | 2014-01-08 |
| EP1793798B1 (en) | 2016-04-20 |
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